CN108473453B - Process for the epoxidation of olefins - Google Patents
Process for the epoxidation of olefins Download PDFInfo
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- CN108473453B CN108473453B CN201780006676.3A CN201780006676A CN108473453B CN 108473453 B CN108473453 B CN 108473453B CN 201780006676 A CN201780006676 A CN 201780006676A CN 108473453 B CN108473453 B CN 108473453B
- Authority
- CN
- China
- Prior art keywords
- hydrogen peroxide
- solvent
- olefin
- chelating agent
- epoxidation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000006735 epoxidation reaction Methods 0.000 title claims abstract description 41
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 36
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 127
- 239000002904 solvent Substances 0.000 claims abstract description 65
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002738 chelating agent Substances 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010936 titanium Substances 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000010457 zeolite Substances 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract 1
- 239000012224 working solution Substances 0.000 description 21
- 239000002244 precipitate Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 12
- 238000005984 hydrogenation reaction Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 11
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 10
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 9
- 150000004056 anthraquinones Chemical class 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000004053 quinones Chemical class 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 3
- UMWZLYTVXQBTTE-UHFFFAOYSA-N 2-pentylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(CCCCC)=CC=C3C(=O)C2=C1 UMWZLYTVXQBTTE-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- HXQPUEQDBSPXTE-UHFFFAOYSA-N Diisobutylcarbinol Chemical compound CC(C)CC(O)CC(C)C HXQPUEQDBSPXTE-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000895 extractive distillation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- IMXBRVLCKXGWSS-UHFFFAOYSA-N methyl 2-cyclohexylacetate Chemical compound COC(=O)CC1CCCCC1 IMXBRVLCKXGWSS-UHFFFAOYSA-N 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- SNDGLCYYBKJSOT-UHFFFAOYSA-N 1,1,3,3-tetrabutylurea Chemical compound CCCCN(CCCC)C(=O)N(CCCC)CCCC SNDGLCYYBKJSOT-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- -1 polysiloxanes Polymers 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 description 2
- 125000004151 quinonyl group Chemical group 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- ZTORCDJTFKLKCU-UHFFFAOYSA-N 1-(4-methylpentyl)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CCCC(C)C ZTORCDJTFKLKCU-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- VKAMZEDHHWTTNZ-UHFFFAOYSA-N 1-octylazepan-2-one Chemical compound CCCCCCCCN1CCCCCC1=O VKAMZEDHHWTTNZ-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- PCFMUWBCZZUMRX-UHFFFAOYSA-N 9,10-Dihydroxyanthracene Chemical compound C1=CC=C2C(O)=C(C=CC=C3)C3=C(O)C2=C1 PCFMUWBCZZUMRX-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009904 heterogeneous catalytic hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000004690 nonahydrates Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
- C07B41/04—Formation or introduction of functional groups containing oxygen of ether, acetal or ketal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Epoxy Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a process for the epoxidation of an olefin with hydrogen peroxide in the presence of a solvent, wherein a mixture comprising the olefin, an aqueous hydrogen peroxide solution and the solvent is continuously passed through a fixed bed of an epoxidation catalyst comprising a titanium zeolite, and a chelating agent is added to the aqueous hydrogen peroxide solution before mixing with the solvent, to reduce or prevent the formation of deposits on the catalyst and the clogging of the pores of the liquid distributor.
Description
Technical Field
The present invention relates to a process for the epoxidation of an olefin, in which process a mixture comprising the olefin, hydrogen peroxide and a solvent is passed continuously through a fixed bed of an epoxidation catalyst comprising a titanium zeolite.
Background
It is known from EP 0100119 a1 to catalyze the liquid-phase epoxidation of olefins with hydrogen peroxide by means of a fixed-bed titanium silicalite catalyst. The reaction is usually carried out in a methanol solvent to achieve high reaction rate and product selectivity. Continuous epoxidation is achieved by passing a mixture comprising an olefin, hydrogen peroxide and methanol over a fixed bed of an epoxidation catalyst as described in WO 99/28029, WO 01/10855 and EP 1085017 a 1.
EP 757045 a1 teaches that in an epoxidation process in which an olefin is reacted with hydrogen peroxide in the presence of a titanium-containing molecular sieve catalyst and a salt, the tendency of the catalyst to generate oxygen with age due to non-selective decomposition of the hydrogen peroxide can be counteracted by the addition of a chelating agent. Polyphosphonic acids and their alkali metal, alkaline earth metal and ammonium salts can be used as chelating agents. EP 757045 a1 discloses the epoxidation of propene with extrudates containing TS-1 titanium silicalite in a continuously stirred reactor wherein aminotrimethylene phosphonic acid is added to a feed stream containing 2.5% by weight hydrogen peroxide, 73% by weight isopropanol, 24% by weight water, 0.2% by weight methanol, 0.29% by weight acetic acid and 0.1% by weight formic acid.
Disclosure of Invention
It has now been found that during prolonged operation of such continuous epoxidation, deposits are formed on the catalyst which cannot be removed by conventional catalyst regeneration procedures by washing or heating with a solvent. These deposits reduce the catalyst activity and can cause uneven liquid distribution in the fixed bed of catalyst, resulting in uneven temperature distribution in the fixed bed, which can impair epoxide selectivity. When a tube bundle reactor is used and a mixture comprising hydrogen peroxide and solvent is dispensed into the tubes through the holes of the liquid distributor, similar deposits can form or accumulate at the holes, and clogging of the holes by the deposits can cause uneven distribution of liquid to the individual tubes.
It has also been found that the formation of such deposits can be reduced or avoided by adding a chelating agent to the aqueous hydrogen peroxide solution prior to mixing with the solvent.
The subject of the present invention is therefore a process for the epoxidation of olefins with hydrogen peroxide in the presence of a solvent, wherein the hydrogen peroxide is used as aqueous hydrogen peroxide, a chelating agent is added to the aqueous hydrogen peroxide before mixing with the solvent, and the mixture comprising the olefin, the solvent and the hydrogen peroxide to which the chelating agent has been added is passed continuously through a fixed bed of an epoxidation catalyst comprising a titanium zeolite.
Detailed Description
In the process of the present invention, a mixture comprising an olefin, hydrogen peroxide and a solvent is continuously passed over a fixed bed of an epoxidation catalyst comprising a titanium zeolite.
The olefin is preferably an unbranched olefin, more preferably an unbranched C2-C6 olefin. The olefin may be substituted, for example allyl chloride. Most preferably, the olefin is propylene. Propylene may be used in combination with propane, preferably in a molar ratio of propane to propylene of 0.001 to 0.15, more preferably 0.08 to 0.12.
The hydrogen peroxide used in the process of the invention is an aqueous hydrogen peroxide solution. The hydrogen peroxide concentration of the aqueous hydrogen peroxide solution is preferably 20 to 85% by weight, more preferably 40 to 70% by weight. The combined amount of water and hydrogen peroxide is preferably higher than 95% by weight, more preferably higher than 99% by weight. The aqueous hydrogen peroxide solution preferably comprises phosphoric acid or an alkali metal or ammonium salt of phosphoric acid, most preferably phosphoric acid in a concentration of 50 to 1000ppm by weight. The aqueous hydrogen peroxide solution may further contain pyrophosphoric acid or an alkali metal or ammonium salt of pyrophosphoric acid.
The aqueous hydrogen peroxide solution is preferably prepared by the anthraquinone process. The anthraquinone process uses a working solution comprising at least one 2-alkylanthraquinone, 2-alkyltetrahydroanthraquinone, or a mixture of both (hereinafter referred to as quinones), and at least one solvent for dissolving the quinones and hydroquinones. The 2-alkylanthraquinone is preferably 2-Ethylanthraquinone (EAQ), 2-amylanthraquinone (AAQ) or 2 (4-methylpentyl) -anthraquinone (IHAQ), more preferably a mixture of EAQ and AAQ and/or IHAQ, wherein the mole fraction of ethyl-bearing quinones is 0.05-0.95. The working solution preferably further comprises the corresponding 2-alkyltetrahydroanthraquinone, and the ratio of 2-alkyltetrahydroanthraquinone plus 2-alkyltetrahydroanthrahydroquinone to 2-alkylanthraquinone plus 2-alkylanthrahydroquinone is preferably maintained in the range of 1 to 20 by adjusting the conditions of the hydrogenation and regeneration steps used in the anthraquinone process. The working solution preferably comprises an alkylbenzene having 9 or 10 carbon atoms as anthraquinone solvent and at least one polar solvent selected from the group consisting of Diisobutylcarbinol (DiBC), Methylcyclohexylacetate (MCA), trioctyl phosphate (TOP), Tetrabutylurea (TBU) and N-octylcaprolactam as anthrahydroquinone solvent, preferably DiBC, MCA and TOP, most preferably TOP.
The anthraquinone process is a cyclic process comprising a hydrogenation stage in which hydrogen is reacted with a working solution in the presence of a hydrogenation catalyst to convert at least part of the quinone to the corresponding hydroquinone, a subsequent oxidation stage in which the hydrogenated working solution containing hydroquinone is reacted with oxygen to form hydrogen peroxide and quinone, and an extraction stage in which hydrogen peroxide is extracted from the oxidized working solution with water to produce an aqueous hydrogen peroxide solution, the extracted working solution being returned to the hydrogenation stage to complete the reaction cycle.
In the hydrogenation stage, the working solution is reacted with hydrogen in the presence of a heterogeneous hydrogenation catalyst. During the reaction, all or part of the quinone is converted to the corresponding hydroquinone. All hydrogenation catalysts known from the prior art for the anthraquinone recycle process can be used as catalysts in the hydrogenation stage. The noble metal catalyst containing palladium is preferred as the main component. The catalyst can be used as a fixed bed catalyst or as a suspended catalyst, which can be an unsupported catalyst such as palladium black or a supported catalyst, of which a suspended supported catalyst is preferred. SiO 22、TiO2、Al2O3And mixed oxides thereof, and zeolite, BaSO4Alternatively, polysiloxanes can be used as support materials for fixed bed catalysts or supported suspension catalysts, preference being given to TiO2And SiO2/TiO2Mixed oxides. It is also possible to use catalysts in the form of structured or honeycomb shaped articles, the surface of which is coated with noble metals. The hydrogenation can be carried out in stirred tank reactors, tubular reactors, fixed bed reactors, loop reactors or gas-lift reactors, which can be equipped with devices for distributing hydrogen in the working solution, such as static mixers or nozzles. Preferably, a tubular reactor with a recycle stream for injecting hydrogen into the reactor feed and a venturi nozzle as known from WO 02/34668 is used. The hydrogenation is carried out at a temperature of 20 to 100 ℃, preferably 45 to 75 ℃, and a pressure of 0.1 to 1MPa, preferably 0.2 to 0.5 MPa. The hydrogenation is preferably carried out in such a way that essentially all of the hydrogen introduced into the hydrogenation reactor is consumed in a single pass reactor. The ratio of hydrogen to working solution fed to the hydrogenation reactor is preferably selected to convert 30-80% of the quinone to the corresponding hydroquinone. If a mixture of 2-alkylanthraquinone and 2-alkyltetrahydroanthraquinone is used, the ratio between hydrogen and working solution is preferably chosen such that only 2-alkyltetrahydroanthraquinone is converted into hydroquinone, while 2-alkylanthraquinone remains in the quinone form.
In the oxidation stage, the hydrogenated working solution is reacted with an oxygen-containing gas, preferably air or oxygen-enriched air. All oxidation reactors known from the prior art for the anthraquinone process can be used for the oxidation, preference being given to bubble columns which are operated cocurrently. The bubble column may have no internal means, but preferably comprises distribution means in the form of packing or sieve trays, most preferably a combination of sieve trays and internal coolers. The oxidation is carried out at a temperature of 30 to 70 ℃, preferably 40 to 60 ℃. The oxidation is preferably carried out with an excess of oxygen to convert more than 90%, preferably more than 95%, of the hydroquinone to the quinone form.
In the extraction stage, the oxidized working solution containing dissolved hydrogen peroxide is extracted with an aqueous solution to obtain an aqueous hydrogen peroxide solution and an extracted oxidized working solution substantially free of hydrogen peroxide. Deionized water is preferably used for extracting hydrogen peroxide, which may optionally contain additives for stabilizing the hydrogen peroxide, adjusting the pH and/or preventing corrosion. The aqueous solution for extracting hydrogen peroxide from the working solution preferably contains phosphoric acid at a concentration of 50 to 500ppm by weight. The extraction is preferably carried out in a countercurrent continuous extraction column, most preferably a sieve tray column. The extracted aqueous hydrogen peroxide solution may be directly used for epoxidation, or may be concentrated to a concentration of preferably 40 to 70% by weight by distilling off water under low pressure. The aqueous hydrogen peroxide solution obtained by the extraction may also be purified, preferably by washing with a solvent, preferably a solvent contained in the working solution.
The anthraquinone process preferably comprises at least one additional stage for regenerating the working solution, in which the by-products formed in the process are converted back to quinones. Regeneration is carried out by treating the hydrogenated working solution with alumina or sodium hydroxide, preferably using a side stream to the recycle process. In addition to the regeneration of the hydrogenated working solution, the extracted oxidized working solution may be regenerated in a side stream using alumina, sodium hydroxide or an organic amine. Suitable methods for regenerating the working solution of the anthraquinone process are well known in the art.
In the process of the present invention, an olefin is reacted with hydrogen peroxide in a solvent. All solvents which are not oxidized or are oxidized only to a small extent by hydrogen peroxide under the reaction conditions selected and are soluble in water in amounts of more than 10% by weight are suitable. Preferably a solvent that is completely miscible with water. Suitable solvents are: alcohols such as methanol, ethanol or tert-butanol; glycols such as ethylene glycol, 1, 2-propylene glycol or 1, 3-propylene glycol; cyclic ethers such as tetrahydrofuran, dioxane or propylene oxide; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, or propylene glycol monomethyl ether; ketones such as acetone or 2-butanone; and nitriles such as acetonitrile and propionitrile. Preferably, the solvent is a methanol solvent. The methanol solvent may be technical grade methanol, a methanol solvent stream recovered in the processing of the epoxidation reaction mixture, or a mixture of the two. The methanol solvent may comprise small amounts of other solvents, such as ethanol, wherein the amount of such other solvents is preferably less than 2% by weight. The solvent is preferably used for epoxidation in a weight ratio of 0.5 to 20 relative to the sum of the weight of water and hydrogen peroxide.
The olefin is preferably used in a molar ratio of olefin to hydrogen peroxide of 1.1:1 to 30:1, more preferably 2:1 to 10:1, and most preferably 3:1 to 5: 1. The epoxidation reaction is preferably carried out at a temperature of 20 to 80 ℃ and more preferably at a temperature of 25 to 60 ℃. The epoxidation reaction is preferably carried out at a pressure above the vapor pressure of the olefin at the reaction temperature so that the olefin remains dissolved in the solvent or exists as a separate liquid phase. The epoxidation reaction is preferably carried out with addition of ammonia in order to increase the epoxide selectivity as described in EP 0230949 a 2. The ammonia is preferably added in an amount of 100 to 3000ppm based on the weight of the hydrogen peroxide.
When the olefin is propylene, the pressure in the epoxidation reaction is preferably 1.9 to 5.0MPa, more preferably 2.1 to 3.6MPa, and most preferably 2.4 to 2.8 MPa. The propylene is preferably in excess sufficient to maintain an additional propylene-rich liquid phase throughout the epoxidation reaction. The use of excess propylene at high pressure provides high reaction rates and hydrogen peroxide conversion, along with high propylene oxide selectivity.
A shaped catalyst may contain 1 to 99% of a binder or support material, all binders and support materials being suitable which do not react with hydrogen peroxide or propylene oxide under the reaction conditions employed for epoxidation, silica being a preferred binder, extrudates of 1 to 5mm diameter are preferably used as fixed bed catalysts, the amount of catalyst used may vary within wide limits, preferably being selected such that a hydrogen peroxide consumption of more than 90%, more preferably more than 95% is achieved within 1 minute to 5 hours under the epoxidation reaction conditions employed.
The epoxidation is preferably carried out in a fixed bed reactor equipped with cooling means and cooled with a liquid cooling medium. When the olefin is propylene, the temperature distribution along the length of the catalyst fixed bed is preferably adjusted so that 70 to 98%, preferably 80 to 95%, of the reaction temperature along the length of the catalyst fixed bed is maintained within a range of less than 5 ℃, preferably within a range of 0.5 to 3 ℃. The temperature of the cooling medium fed to the cooling device is preferably adjusted to a value 3 to 13 ℃ lower than the highest temperature in the catalyst fixed bed. The epoxidation reaction mixture is preferably passed through the catalyst bed in a downflow mode, preferably with a superficial flow velocity of from 1 to 100m/h, more preferably from 5 to 50m/h, most preferably from 5 to 30 m/h. The superficial flow velocity is defined as the ratio of the volumetric flow to the cross-section of the catalyst bed. In addition, the reaction mixture is preferably used for 1 to 20 hours-1Preferably 1.3 to 15 hours-1Is disclosed in WO 02/085873, page 8, line 23 to page 9, line 15, using excess propylene providing a reaction mixture comprising two liquid phases, a solvent-rich phase and a propylene-rich liquid phase, the epoxidation reaction most preferably being carried out with a fixed bed of catalyst maintained in a trickle bed state at a pressure close to the vapor pressure of the propylene at the reaction temperatureThe treatment with the heated gas, preferably an oxygen-containing gas, or by solvent washing, preferably by periodic regeneration as described in WO 2005/000827. Different regeneration methods may also be combined.
In the process of the present invention, the chelating agent is added to the aqueous hydrogen peroxide solution before mixing with the solvent. Preferably, the chelating agent is added and then the aqueous hydrogen peroxide solution is mixed with at least 50% of the solvent used to react the olefin with the hydrogen peroxide, more preferably with at least 80% of the solvent. In principle, any Fe capable of coordinating through at least two coordinating atoms3+Preferably, hydroxycarboxylic acids (i.e., compounds containing carboxylic acid groups and hydroxyl groups on the same or adjacent carbon atoms), polycarboxylic acids (i.e., compounds containing at least two carboxylic acid groups) or polyphosphonic acids (i.e., compounds containing at least two phosphonic acid groups), or alkali metal or ammonium salts of hydroxycarboxylic acids, polycarboxylic acids or polyphosphonic acids are used as chelating agents-7～10-2The amount of chelating agent added on a molar basis.
The addition of a chelating agent to an aqueous solution of hydrogen peroxide and then mixing it with a solvent reduces or prevents the formation of insoluble deposits on the titanium zeolite epoxidation catalyst that reduce catalyst activity and can lead to maldistribution of liquid in the fixed bed of catalyst. It also reduces or prevents plugging of the holes of the liquid distributor used to distribute aqueous hydrogen peroxide to the tubes of the tube bundle reactor used for the epoxidation reaction, which plugging can result in uneven liquid distribution to the individual tubes. The addition of chelating agents is particularly effective in preventing the formation of deposits resulting from metallic impurities in the feedstock, such as metal hydroxide and hydrous oxide deposits or metal phosphate deposits.
The mixture obtained by mixing the solvent with the aqueous hydrogen peroxide solution to which the chelating agent is added is preferably mixed with the olefin before being contacted with the fixed bed epoxidation catalyst. Mixing may be carried out by turbulence in the feed line or in a dedicated mixer such as a static mixer. Mixing can also be achieved by passing the mixture, olefin, and optionally other feed streams through an inert solid layer, such as a layer of glass beads, disposed upstream of the fixed bed epoxidation catalyst.
In a preferred embodiment of the invention, the fixed bed epoxidation catalyst is placed in the tubes of a vertically arranged tube bundle reactor, a chelating agent is added to the aqueous hydrogen peroxide stream to form a mixed stream before it is mixed with the solvent stream, and the mixed stream is distributed to the top of the tubes through the holes of the liquid distributor. The flow rate of the stream and the reaction conditions are preferably selected to maintain the catalyst bed in a trickle bed state as described above. Suitable liquid dispensers are known in the art and are commercially available. The mixed stream may be combined with the olefin before it is distributed to the top of the tube, which is preferred if the mixture formed by mixing the mixed stream with the olefin forms a single liquid phase. Alternatively, the combined stream and olefin may be distributed to the top of the tube through the orifices of two separate liquid distributors, which is preferred when the olefin is used in an amount that exceeds its solubility in the combined stream. Suitable liquid distributors for independently distributing two liquids to the reaction tubes of a tube bundle reactor are known from the prior art, for example from WO 2005/025716.
The olefin oxide formed by the epoxidation reaction may be separated from the epoxidation reaction mixture by methods known in the art, such as by distillation or extractive distillation. When the olefin is propylene and the solvent is a methanol solvent, the propylene oxide is preferably separated from the epoxidation reaction mixture by distillation after a pressure release stage in which most of the unreacted propylene is removed. The distillation is preferably carried out in at least two columns, the first column being operated to obtain a crude propene oxide overhead product containing from 20 to 60% of the methanol contained in the epoxidation reaction mixture, and the overhead product being further purified by at least one further distillation. The overhead product is preferably further purified by extractive distillation after distilling off residual propene and propane, most preferably using the extractive distillation process of WO2004/048355 for additional carbonyl compound removal.
Examples
Example 1 (comparative example)
500g of iron (III) chloride containing 436mg/kg (150mg/kg Fe)3+) 57% by weight aqueous hydrogen peroxide was mixed with a methanol solvent consisting of 1900g methanol, 150g water and 850mg ammonia. The solid precipitated, filtered, dried and weighed. The weight of the dried precipitate was 226 mg.
Example 2
Example 1 was repeated, but 50g of a 1% by weight aqueous solution of HEDP was added to the aqueous hydrogen peroxide solution before mixing with the methanol solvent. The solid precipitated, filtered, dried and weighed. The weight of the dried precipitate was 39 mg.
This example shows that the addition of a chelating agent to an aqueous hydrogen peroxide solution greatly reduces the precipitate formed from iron salt impurities.
Example 3 (comparative example)
Example 2 was repeated except that instead of adding the aqueous HEDP solution to the aqueous hydrogen peroxide solution, the aqueous HEDP solution was added after mixing the aqueous hydrogen peroxide solution with the methanol solvent. The solid precipitated, filtered, dried and weighed. The weight of the dried precipitate was 135 mg.
This example shows that adding a chelating agent after mixing an aqueous hydrogen peroxide solution with a solvent is less efficient than adding a chelating agent to an aqueous hydrogen peroxide solution before mixing with a solvent.
Example 4 (comparative example)
Example 2 was repeated, but instead of adding the aqueous HEDP solution to the aqueous hydrogen peroxide solution, the aqueous HEDP solution was added to the methanol solvent prior to mixing with the aqueous hydrogen peroxide solution. The solid precipitated, filtered, dried and weighed. The weight of the dried precipitate was 130 mg.
This example shows that the addition of a chelating agent to a solvent is less efficient than the addition of a chelating agent to an aqueous hydrogen peroxide solution.
Example 5
Example 2 was repeated, but 875mg of citric acid was added to the aqueous hydrogen peroxide solution instead of the aqueous HEDP solution. The solid precipitated, filtered, dried and weighed. The weight of the dried precipitate was 118 mg.
Example 6 (comparative example)
A nonahydrate containing 572mg/kg of aluminum (III) nitrate (72.5mg/kg of Al) was used3+) Example 1 was repeated instead of the aqueous solution of iron (III) chloride in hydrogen peroxide. The solid precipitated, filtered, dried and weighed. The weight of the dried precipitate was 67 mg.
Example 7
Example 6 was repeated, but 50g of a 1% by weight aqueous solution of HEDP was added to the aqueous hydrogen peroxide solution before mixing with the methanol solvent. No solid precipitated.
This example shows that the addition of a chelating agent to aqueous hydrogen peroxide prevents the formation of precipitates from aluminum salt impurities.
Example 8 (comparative example)
500g of iron (III) chloride containing 436mg/kg (150mg/kg Fe)3+) 57% by weight aqueous hydrogen peroxide was mixed with an acetonitrile solvent consisting of 1900g acetonitrile, 150g water and 850mg ammonia. The solid precipitated, filtered, dried and weighed. The weight of the dried precipitate was 27 mg.
Example 9
Example 8 was repeated, but 50g of a 1% by weight aqueous solution of HEDP was added to the aqueous hydrogen peroxide solution before mixing with the acetonitrile solvent. The solid precipitated, filtered, dried and weighed. The weight of the dried precipitate was 23 mg.
Example 10 (comparative example)
Example 1 was repeated, but using an ethanol solvent consisting of 1900g of ethanol, 150g of water and 850mg of ammonia, instead of the methanol solvent. The solid precipitated, filtered, dried and weighed. The weight of the dried precipitate was 123 mg.
Example 11
Example 10 was repeated, but 50g of a 1% by weight aqueous solution of HEDP was added to the aqueous hydrogen peroxide solution before mixing with the ethanol solvent. The solid precipitated, filtered, dried and weighed. The weight of the dried precipitate was 77 mg.
Example 12 (comparative example)
Example 1 was repeated, but using a 2-propanol solvent consisting of 1900g of 2-propanol, 150g of water and 850mg of ammonia instead of the methanol solvent. The solid precipitated, filtered, dried and weighed. The weight of the dried precipitate was 57 mg.
Example 13
Example 12 was repeated, but 50g of a 1% by weight aqueous solution of HEDP was added to the aqueous hydrogen peroxide solution before mixing with the 2-propanol solvent. The solid precipitated, filtered, dried and weighed. The weight of the dried precipitate was 48 mg.
Examples 8-13 show that the addition of a chelating agent to aqueous hydrogen peroxide reduces the formation of precipitates from iron salt impurities for different kinds of solvents.
Claims (11)
1. Process for the epoxidation of an olefin with hydrogen peroxide in the presence of a solvent, wherein the solvent is selected from methanol, ethanol and acetonitrile, the hydrogen peroxide is used as aqueous hydrogen peroxide solution to which a chelating agent is added before mixing with the solvent, the mixture comprising the olefin, the solvent and the hydrogen peroxide to which the chelating agent is added being continuously passed through a fixed bed of an epoxidation catalyst comprising a titanium zeolite, wherein the chelating agent is selected from polyphosphonic acids and their alkali metal and ammonium salts.
2. The method of claim 1, wherein the aqueous hydrogen peroxide solution comprises phosphoric acid or an alkali metal or ammonium salt of phosphoric acid.
3. A process according to claim 1 or 2, wherein the aqueous hydrogen peroxide solution is mixed with at least 50% of a solvent for reacting the olefin with hydrogen peroxide.
4. A process according to claim 1 or 2, wherein the chelating agent is present at 10 per mole of hydrogen peroxide-7～10-2The amount of chelating agent added on a molar basis.
5. The process of claim 1 or 2, wherein the olefin is propylene.
6. The method of claim 1 or 2, wherein the solvent is a methanol solvent.
7. The process of claim 1 or 2, wherein the mixture passed over the fixed bed of epoxidation catalyst comprises ammonia.
8. The method of claim 7, wherein the mixture comprises ammonia in an amount of 100 to 3000ppm based on the weight of hydrogen peroxide.
9. The process of claim 1 or 2, wherein the fixed bed epoxidation catalyst is placed in the tubes of a vertically arranged tube bundle reactor, a chelating agent is added to the aqueous hydrogen peroxide stream, which is then mixed with a solvent stream to form a mixed stream, which is distributed to the top of the tubes through the holes of a liquid distributor.
10. The method of claim 9, wherein the mixed stream is mixed with the olefin and then distributed to the top of the tube.
11. The method of claim 9, wherein the combined stream and olefin are distributed to the top of the tube through the orifices of two separate liquid distributors.
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| EP16151786 | 2016-01-19 | ||
| EP16151786.7 | 2016-01-19 | ||
| PCT/EP2017/050236 WO2017125266A1 (en) | 2016-01-19 | 2017-01-06 | Process for the epoxidation of an olefin |
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| EP (1) | EP3405460B1 (en) |
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| WO2017089074A1 (en) | 2015-11-26 | 2017-06-01 | Evonik Degussa Gmbh | Process for the epoxidation of an olefin |
| CN108884065B (en) | 2016-03-21 | 2022-06-07 | 赢创运营有限公司 | Process for epoxidation of propene |
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| KR102441642B1 (en) | 2015-02-17 | 2022-09-07 | 에보닉 오퍼레이션스 게엠베하 | Method for the epoxidation of an olefin with hydrogen peroxide |
| EP3059230A1 (en) | 2015-02-17 | 2016-08-24 | Evonik Degussa GmbH | Method for the epoxidation of propene with hydrogen peroxide |
| PL3288927T3 (en) | 2015-04-28 | 2020-03-31 | Evonik Degussa Gmbh | Process for the epoxidation of propene |
| CN108779053B (en) | 2015-11-25 | 2021-08-31 | 赢创运营有限公司 | Process for producing propylene glycol from propylene and hydrogen peroxide |
| TWI707847B (en) | 2015-11-26 | 2020-10-21 | 德商贏創運營有限公司 | Process for the epoxidation of propene |
| WO2017089074A1 (en) | 2015-11-26 | 2017-06-01 | Evonik Degussa Gmbh | Process for the epoxidation of an olefin |
| EP3380460B1 (en) | 2015-11-26 | 2021-04-21 | Evonik Operations GmbH | Process and reactor for the epoxidation of propene |
| CN108884065B (en) | 2016-03-21 | 2022-06-07 | 赢创运营有限公司 | Process for epoxidation of propene |
-
2017
- 2017-01-06 EP EP17700124.5A patent/EP3405460B1/en active Active
- 2017-01-06 MY MYPI2018702491A patent/MY183767A/en unknown
- 2017-01-06 ES ES17700124T patent/ES2804208T3/en active Active
- 2017-01-06 US US16/070,873 patent/US10676450B2/en active Active
- 2017-01-06 CN CN201780006676.3A patent/CN108473453B/en active Active
- 2017-01-06 KR KR1020187023326A patent/KR102625924B1/en active IP Right Grant
- 2017-01-06 WO PCT/EP2017/050236 patent/WO2017125266A1/en active Application Filing
- 2017-01-06 EA EA201891625A patent/EA037936B1/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1149053A (en) * | 1995-08-02 | 1997-05-07 | 阿科化学技术公司 | Improved epoxidation process |
| EP0940393B1 (en) * | 1998-03-05 | 2002-07-17 | Enichem S.p.A. | Process for the preparation of olefinic epoxides |
| EP1346986A1 (en) * | 2002-03-18 | 2003-09-24 | Degussa AG | Process for the epoxidation of olefins |
| CN1684904A (en) * | 2002-09-30 | 2005-10-19 | 德古萨股份公司 | Novel aqueous hydrogen peroxide solutions |
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|---|---|
| EA201891625A1 (en) | 2019-01-31 |
| ES2804208T3 (en) | 2021-02-04 |
| MY183767A (en) | 2021-03-12 |
| CN108473453A (en) | 2018-08-31 |
| KR20180101531A (en) | 2018-09-12 |
| TW201730169A (en) | 2017-09-01 |
| AR107438A1 (en) | 2018-05-02 |
| TWI752935B (en) | 2022-01-21 |
| EP3405460B1 (en) | 2020-06-24 |
| KR102625924B1 (en) | 2024-01-16 |
| US20190023673A1 (en) | 2019-01-24 |
| WO2017125266A1 (en) | 2017-07-27 |
| HUE050560T2 (en) | 2020-12-28 |
| US10676450B2 (en) | 2020-06-09 |
| EA037936B1 (en) | 2021-06-09 |
| EP3405460A1 (en) | 2018-11-28 |
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